2 research outputs found
Spectroscopic, Morphological and Mechanistic Investigation of the Solvent.Promoted Aggregation of Porphyrins Modified in meso-positions by Glucosylated steroids
Solvent-driven aggregation
of a series of porphyrin derivatives was
studied by UV/Vis and circular dichroism
spectroscopy. The porphyrins are
characterised by the presence in the
meso positions of steroidal moieties
further conjugated with glucosyl
groups. The presence of these groups
makes the investigated macrocycles
amphiphilic and soluble in aqueous solvent,
namely, dimethyl acetamide/
water. Aggregation of the macrocycles
is triggered by a change in bulk solvent
composition leading to formation of
large architectures that express supramolecular
chirality, steered by the presence
of the stereogenic centres on the
periphery of the macrocycles. The aggregation
behaviour and chiroptical
features of the aggregates are strongly
dependent on the number of moieties
decorating the periphery of the porphyrin
framework. In particular, experimental
evidence indicates that the
structure of the steroid linker dictates
the overall chirality of the supramolecular
architectures. Moreover, the porphyrin
concentration strongly affects
the aggregation mechanism and the
CD intensities of the spectra. Notably,
AFM investigations reveal strong differences
in aggregate morphology that
are dependent on the nature of the appended
functional groups, and closely
in line with the changes in aggregation
mechanism. The suprastructures
formed at lower concentration show a
network of long fibrous structures
spanning over tens of micrometres,
whereas the aggregates formed at
higher concentration have smaller rodshaped
structures that can be recognised
as the result of coalescence of
smaller globular structures. The fully
steroid substituted derivative forms
globular structures over the whole concentration
range explored. Finally, a rationale
for the aggregation phenomena
was given by semiempirical calculations
at the PM6 level
Spectroscopic, Morphological and Mechanistic Investigation of the Solvent.Promoted Aggregation of Porphyrins Modified in meso-positions by Glucosylated steroids
Solvent-driven aggregation
of a series of porphyrin derivatives was
studied by UV/Vis and circular dichroism
spectroscopy. The porphyrins are
characterised by the presence in the
meso positions of steroidal moieties
further conjugated with glucosyl
groups. The presence of these groups
makes the investigated macrocycles
amphiphilic and soluble in aqueous solvent,
namely, dimethyl acetamide/
water. Aggregation of the macrocycles
is triggered by a change in bulk solvent
composition leading to formation of
large architectures that express supramolecular
chirality, steered by the presence
of the stereogenic centres on the
periphery of the macrocycles. The aggregation
behaviour and chiroptical
features of the aggregates are strongly
dependent on the number of moieties
decorating the periphery of the porphyrin
framework. In particular, experimental
evidence indicates that the
structure of the steroid linker dictates
the overall chirality of the supramolecular
architectures. Moreover, the porphyrin
concentration strongly affects
the aggregation mechanism and the
CD intensities of the spectra. Notably,
AFM investigations reveal strong differences
in aggregate morphology that
are dependent on the nature of the appended
functional groups, and closely
in line with the changes in aggregation
mechanism. The suprastructures
formed at lower concentration show a
network of long fibrous structures
spanning over tens of micrometres,
whereas the aggregates formed at
higher concentration have smaller rodshaped
structures that can be recognised
as the result of coalescence of
smaller globular structures. The fully
steroid substituted derivative forms
globular structures over the whole concentration
range explored. Finally, a rationale
for the aggregation phenomena
was given by semiempirical calculations
at the PM6 level